Metallofullerene Gd@C82 offers the opportunity to produce novel and advanced polymer-based nanocomposite materials. In this work, we reported the synthesis of novel Gd@C82-containing copolymers with the optimum condition found by changing the temperature, initiator and fullerene contents of C60-PS. The developed materials, based on polystyrene, displayed unique nanostructures which were confirmed by many measurements (GPC, AFM, SEM, TGA/DSC and NEXAFS analysis). The mechanism, stability and structure of Gd@C82-containing copolymer were discussed. This approach offers a new possibility of optimizing the polymer performance with metallofullerene.